CN116601794A - Positive electrode active material and pole piece, secondary battery, battery module, battery pack and device related to positive electrode active material - Google Patents
Positive electrode active material and pole piece, secondary battery, battery module, battery pack and device related to positive electrode active material Download PDFInfo
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- CN116601794A CN116601794A CN202180071747.4A CN202180071747A CN116601794A CN 116601794 A CN116601794 A CN 116601794A CN 202180071747 A CN202180071747 A CN 202180071747A CN 116601794 A CN116601794 A CN 116601794A
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- positive electrode
- electrode active
- active material
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present application provides a positive electrode active material comprising an a material as described below and a B material as described below, wherein the a material is at least one selected from the following single crystal materials or single crystal-like materials: li (Li) x M y (PO 4 ) z M is selected from one or more of Ni, co, mn, fe, mg, al, V, zn, zr, F, v is the valence of M, x is not less than 1 and not more than 3, z is not less than 1 and not more than 3, and x+vy-3 z=0; the Dv50 of the a material is 0.8 μm to 4.2 μm; the material B is at least one of the following materials: (i) LiAO 2 A is Ni, co or Mn; or (ii) LiNi a Co b E 1‑a‑b O 2 E is selected from at least one of Mn and Al, a is more than or equal to 0.50 and less than or equal to 0.98,0.001, b is more than or equal to 0.3; wherein the a material is present in a mixing proportion m of 50 to 97 wt% based on the total weight of the positive electrode active material. The positive electrode active material has the advantages of low cost, good safety, long cycle life, high energy density and the like.
Description
The application relates to the technical field of lithium batteries, in particular to a positive electrode active material, a positive electrode plate, a secondary battery, a battery module, a battery pack and an electric device.
Currently, lithium ion secondary batteries generally use ternary materials (e.g., nickel cobalt lithium manganate (NCM), nickel cobalt lithium aluminate (NCA)) or quaternary materials (e.g., nickel cobalt manganese lithium aluminate (NCMA)) as positive electrode active materials. However, the material has the advantages of energy density, and also has the defects of high price, short cycle life, poor safety and the like.
Lithium iron phosphate (LFP) is gradually and widely used by virtue of its low cost, good safety and the like. However, the energy density of such materials is not always satisfactory. The improved lithium iron manganese phosphate (LMFP) has a very limited improvement range, although the energy density is improved while the advantages of good safety, long service life and the like of the LFP are maintained.
Currently, there is a need in the art for a more desirable positive electrode active material that should have a balance of properties, i.e., be cost effective, safe, and at least one of good cycle life and improved energy density.
Disclosure of Invention
The present application has been made in view of the above problems, and an object thereof is to provide a positive electrode active material which is cost-effective, safe, has an improved cycle life, and has an improved balance of performance in at least one of energy density (in particular, gram capacity).
In order to achieve the above object, the present application provides a positive electrode active material and a pole piece, a secondary battery, a battery module, a battery pack and a device related thereto.
A first aspect of the present application provides a positive electrode active material comprising an a material as described below and a B material as described below, wherein the a material is at least one selected from the following materials:
Li x M y (PO 4 ) z
wherein M is selected from one or more of Ni, co, mn, fe, mg, al, V, zn, zr, F, x is not less than 1 and not more than 3, z is not less than 1 and not more than 3, v is the valence of M, and x+vy-3 z=0;
the material A is monocrystalline material or monocrystalline-like material;
the Dv50 of the a material is 0.8 μm to 4.2 μm, alternatively 0.8 μm to 3.2 μm, more alternatively 0.9 μm to 2.3 μm, still more alternatively 1 μm to 1.5 μm;
the material B is at least one of the following materials:
(i)LiAO 2 a is Ni, co or Mn; and
(ii)LiNi a Co b E 1-a-b O 2 e is selected from at least one of Mn and Al, a is more than or equal to 0.50 and less than or equal to 0.98,0.001, b is more than or equal to 0.3;
The a material is present in a mixing ratio of 50 to 97 wt%, alternatively 65 to 97 wt%, more alternatively 70 to 95 wt%, still more alternatively 80 to 95 wt%, i.e., m, based on the total weight of the positive electrode active material.
Therefore, the positive electrode active material is obtained by mixing a relatively large amount of A materials with a specific B material, and the positive electrode active material has good comprehensive performance: the advantages of the A material such as safety, cost effectiveness and the like are reserved, and the gram capacity is improved compared with that of the A material alone without obviously losing the advantages of the A material in the cycle life.
In any embodiment, in the positive electrode active material of the present application, the B material is present in a mixing proportion of 3 to 50 wt%, alternatively 5 to 30 wt%, based on the total weight of the positive electrode active material. Mixing the B material with the a material in such a mixing ratio can improve the gram capacity of the resulting positive electrode active material over the a material alone without significantly losing the advantages of the a material in terms of cycle life.
In any embodiment, in the positive electrode active material of the present application, the a material is selected from at least one of:
Lithium iron manganese phosphate or lithium iron phosphate, the chemical formula is LiMn d Fe 1-d PO 4 D is more than or equal to 0 and less than or equal to 0.9, alternatively, d is more than or equal to 0.1 and less than or equal to 0.9, and still more alternatively, d is more than or equal to 0.1 and less than or equal to 0.8; and
lithium vanadium phosphate of the chemical formula Li 3 V 2 (PO 4 ) 3 。
By further selecting the above materials as the a material, the positive electrode active material of the present application can be made more cost-effective, longer in cycle life, and excellent in safety performance.
In any embodiment, in the positive electrode active material of the present application, the specific surface area (BET) of the a material is 8m 2 /g to 26m 2 /g, optionally 10m 2 /g to 24m 2 /g, more optionally 10m 2 /g to 23m 2 And/g. By controlling the BET of the a material within the above range, the electrochemical reaction area can be effectively limited, thereby reducing and suppressing interfacial side reactions during cycling, reducing the rate of cycle decay, and thus prolonging the cycle life.
In any embodiment, in the positive electrode active material of the present application, (ii) LiNi of the B material a Co b E 1-a-b O 2 Wherein a is more than or equal to 0.5 and less than or equal to 0.98, alternatively, a is more than or equal to 0.50 and less than or equal to 0.90, more alternatively, a is more than or equal to 0.50 and less than or equal to 0.88, and still more alternatively, a is more than or equal to 0.55 and less than or equal to 0.88; and/or b is less than or equal to 0.0050.30, alternatively 0.05.ltoreq.b.ltoreq.0.30, more alternatively 0.05.ltoreq.b.ltoreq.0.20. By controlling a and B in the general formula of the material B within the above-described range, it is useful to further improve the gram capacity and cycle life of the positive electrode active material obtained after mixing the material a with the material B.
In any embodiment, in the positive electrode active material of the present application, (ii) LiNi of the B material a Co b E 1-a-b O 2 Wherein a and b have the following relationship: k= (a+b)/(1-a-b), and 1.5.ltoreq.k.ltoreq.99, alternatively 1.5.ltoreq.k.ltoreq.19. By limiting the coefficient k to the above range, the gram capacity and/or cycle life can be further improved.
In any embodiment, in the positive electrode active material of the present application, (ii) LiNi of the B material a Co b E 1-a-b O 2 Wherein k and m have the following relationship: k.m.gtoreq.1, alternatively k.m.gtoreq.1.1, more alternatively k.m.gtoreq.1.6. When k×m is within the above range, the positive electrode active material has more excellent gram capacity and cycle life.
In any embodiment, in the positive electrode active material of the present application, the B material is LiNi a Co b Mn 1-a-b O 2 、LiNi a Co b Al 1-a-b O 2 、LiNi a Co b Mn c Al 1-a-b-c O 2 Or a combination thereof, wherein a, b are as defined above, 0.01.ltoreq.c.ltoreq.0.34. By selecting the above-described B material, the gram capacity and/or cycle life of the positive electrode active material can be further improved.
In any embodiment, the B material is a single crystal or a single-like crystal material, the particles of which have a Dv50 of 2 μm to 4.5 μm, alternatively 2.1 μm to 4.4 μm, more alternatively 3.5 μm to 4.4 μm; and/or BET of 0.40m 2 /g to 1.20m 2 /g, optionally 0.55m 2 /g to 0.95m 2 /g, more optionally 0.55m 2 /g to 0.89m 2 /g。The gram capacity of the positive electrode active material can be further improved by selecting the material B as defined above.
In any embodiment, the positive electrode active material of the present application, the B material is a secondary particle having a Dv50 of 3.5 μm to 13 μm, alternatively 3.5 μm to 12 μm; and/or a specific surface area of 0.31m 2 /g to 1.51m 2 /g, optionally 0.54m 2 /g to 1.51m 2 And/g. By selecting the secondary particle form B material, the diffusion path and bulk diffusion resistance of lithium ions can be shortened, the polarization of the material can be reduced, the capacity exertion of the positive electrode active material can be improved, and the gram capacity of the positive electrode active material can be improved.
The second aspect of the present application also provides a positive electrode sheet comprising a current collector and a sheet material layer disposed on at least one surface of the current collector, the sheet material layer comprising the positive electrode active material of the first aspect of the present application.
The third aspect of the present application also provides a secondary battery comprising the positive electrode active material of the first aspect of the present application or the positive electrode tab of the second aspect.
The fourth aspect of the application also provides a battery module comprising the secondary battery of the third aspect of the application.
The fifth aspect of the application also provides a battery pack comprising the battery module of the fourth aspect of the application.
The sixth aspect of the application also provides an electric device comprising at least one selected from the secondary battery of the third aspect of the application, the battery module of the fourth aspect, or the battery pack of the fifth aspect.
The positive electrode active material has good comprehensive performance: has the advantages of low cost, good safety, improved energy density (especially gram capacity) and good cycle life.
Fig. 1 is a schematic view of a secondary battery according to an embodiment of the present application.
Fig. 2 is an exploded view of the secondary battery according to an embodiment of the present application shown in fig. 1.
Fig. 3 is a schematic view of a battery module according to an embodiment of the present application.
Fig. 4 is a schematic view of a battery pack according to an embodiment of the present application.
Fig. 5 is an exploded view of the battery pack of the embodiment of the present application shown in fig. 4.
Fig. 6 is a schematic view of an electric device in which a secondary battery according to an embodiment of the present application is used as a power source.
Reference numerals illustrate:
1, a battery pack; 2, upper box body; 3, lower box body; 4, a battery module; 5 a secondary battery; 51 a housing; 52 electrode assembly; 53 roof assembly
Hereinafter, embodiments of the positive electrode active material, the positive electrode tab, the secondary battery, the battery module, the battery pack, and the electrical device of the present application are specifically disclosed with reference to the accompanying drawings as appropriate. However, unnecessary detailed description may be omitted. For example, detailed descriptions of well-known matters and repeated descriptions of the actual same structure may be omitted. This is to avoid that the following description becomes unnecessarily lengthy, facilitating the understanding of those skilled in the art. Furthermore, the drawings and the following description are provided for a full understanding of the present application by those skilled in the art, and are not intended to limit the subject matter recited in the claims.
The "range" disclosed herein is defined in terms of lower and upper limits, with the given range being defined by the selection of a lower and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges that are defined in this way can be inclusive or exclusive of the endpoints, and any combination can be made, i.e., any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3,4 and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present application, unless otherwise indicated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed throughout, and "0-5" is simply a shorthand representation of a combination of these values. When a certain parameter is expressed as an integer of 2 or more, it is disclosed that the parameter is, for example, an integer of 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12 or the like.
All embodiments of the application and alternative embodiments may be combined with each other to form new solutions, unless otherwise specified.
All technical features and optional technical features of the application may be combined with each other to form new technical solutions, unless specified otherwise.
All the steps of the present application may be performed sequentially or randomly, preferably sequentially, unless otherwise specified. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, or may comprise steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), may include steps (a), (c) and (b), may include steps (c), (a) and (b), and the like.
The terms "comprising" and "including" as used herein mean open ended or closed ended, unless otherwise noted. For example, the terms "comprising" and "comprises" may mean that other components not listed may be included or included, or that only listed components may be included or included.
The term "or" is inclusive in this application, unless otherwise specified. For example, the phrase "a or B" means "a, B, or both a and B. More specifically, either of the following conditions satisfies the condition "a or B": a is true (or present) and B is false (or absent); a is false (or absent) and B is true (or present); or both A and B are true (or present).
Currently, a ternary material (e.g., NCM, NCA material) or a quaternary material (e.g., NCMA material) is commonly used as a positive electrode active material for lithium ion secondary batteries—such a material is favored because of its high energy density. However, such materials have many non-negligible disadvantages, such as high price, short cycle life and poor safety, along with energy density advantages.
Under the background, the lithium iron phosphate (LFP) material is gradually and widely applied by virtue of the advantages of low cost, good safety, long cycle life and the like; however, the energy density of such materials is not satisfactory. Lithium iron manganese phosphate (LMFP) materials produced as technological improvements to LFP materials, while improving energy density to some extent, are still not fully satisfactory.
In view of the foregoing, there is a need in the art for a positive electrode active material that is cost effective, safe, and has a balance of properties that is at least one of higher energy density and longer cycle life.
Without being bound by any theory, the inventors of the present application have found that if the energy density of the other positive electrode active materials (e.g., ternary or quaternary materials) with high energy density is improved by mixing the latter with LFP and/or LMFP materials, in most cases, a positive electrode active material with balanced properties is not obtained—mixed arbitrarily, but not only the gram capacity of LFP and/or LMFP materials may not be improved, but even its cycle life advantages may be severely lost (even the cycle life may be unacceptably deteriorated). The material obtained in this way has unbalanced properties and does not have practical application value.
In view of the above problems, the inventors of the present application have proposed a positive electrode active material obtained by blending a specific LFP and/or LMFP material with a specific ternary and/or quaternary material. The positive electrode active material has good comprehensive performance. That is, the positive electrode active material of the present application has improved energy density (particularly gram capacity) compared to LFP and/or LMFP materials alone without significantly increasing cost and without significantly losing cycle life advantages. Even in some cases, the positive electrode active materials of the present application have improved gram capacity and cycle life compared to LFP and/or LMFP materials alone.
Positive electrode active material
In one embodiment of the present application, the present application provides a positive electrode active material including: a material as described below and a material B as described below, wherein
The material A is at least one selected from the following materials:
Li x M y (PO 4 ) z
wherein M is selected from one of Ni, co, mn, fe, mg, al, V, zn, zr, F
One or more species, x is not less than 1 and not more than 3, z is not less than 1 and not more than 3, and v is the valence of M, x+vy-3 z=0;
the material A is monocrystalline material or monocrystalline-like material;
the Dv50 of the a material is 0.8 μm to 4.2 μm;
the material B is at least one of the following materials:
(i)LiAO 2 a is Ni, co or Mn; or (b)
(ii)LiNi a Co b E 1-a-b O 2 E is selected from at least one of Mn and Al, a is more than or equal to 0.50 and less than or equal to 0.98,0.001, b is more than or equal to 0.3;
the a material is present in a mixing ratio of 50 to 97 wt%, i.e., m, based on the total weight of the positive electrode active material.
Without being bound by any theory, the inventors have found that the positive electrode active material of the present application obtained by blending a specific B material in a relatively large amount (not less than 50 wt% based on the total weight of the positive electrode active material) has good overall properties: compared with the single A material, the positive electrode active material provided by the application has the advantages of safety, cost effectiveness and the like of the A material, and the cycle life advantage of the A material is not obviously lost while gram capacity is improved. In particular, in some embodiments, the positive electrode active materials of the present application also have a "synergistic effect" between the a and B materials, such that the resulting positive electrode active material has improved gram capacity and prolonged cycle life compared to the a material alone.
By adopting a single crystal material or a quasi-single crystal material with a Dv50 of 0.8-4.2 μm as the material A, the diffusion path of lithium ions can be shortened, thereby effectively improving the gram capacity exertion and the cycle life of the positive electrode active material.
In some embodiments, optionally, the Dv50 of the a material is 0.8 μm to 3.2 μm, more optionally 0.9 μm to 2.3 μm, still more optionally 1 μm to 1.5 μm. By controlling the Dv50 value of the a material within the above range, the gram capacity and/or cycle life of the positive electrode active material can be further improved.
In some embodiments, in the positive electrode active material of the present application, the a material is present in a mixing ratio, i.e., m, of optionally 65 wt% to 97 wt%, more optionally 70 wt% to 95 wt%, still more optionally 80 wt% to 95 wt%, based on the total weight of the positive electrode active material. By further selecting the mixing ratio of the a material, i.e., m, the gram capacity and/or cycle life of the positive electrode active material of the present application can be further improved.
As used herein, the terms "monocrystalline like particles", "quasi-monocrystalline particles", "monocrystalline material particles" or the like have substantially similar meanings, which means individual particles (i.e. primary particles) and/or agglomerated particles, which are particles formed by agglomeration of not more than 30 (in particular about 5 to 15) primary particles having an average particle size of not less than 0.8 μm (in particular an average particle size in the range of 800nm to 10000 nm).
As used herein, the term "average particle size" is defined as follows: and testing the material by adopting a scanning electron microscope, adjusting a test sample and the amplification factor to ensure that more than 100 primary particles are in the visual field, measuring the size of the particles in the length direction by using a ruler, measuring 100-200 primary particles in total, removing 1/10 particles with the maximum particle size and 1/10 particles with the minimum particle size from the primary particles, and averaging the particle size data of the remaining 8/10 particles to obtain the average particle size.
As used herein, the term "primary particles" means individual particles that are not agglomerated, i.e., what is commonly referred to in the art as "primary particles".
As used herein, the terms "secondary particles" and "polycrystalline material particles" generally have similar meanings, meaning particles formed by agglomeration of more than 30 primary particles having an average particle size of no more than 0.8 μm (particularly an average particle size in the range of 50-800 nm).
As used herein, the term "Dv50" means that 50% by volume of the particles in the powder particle size distribution have a particle size not exceeding the current value; i.e., median particle size; the unit is μm.
As used herein, the term "Dv99" means that 99% by volume of particles in the powder particle size distribution have a particle size not exceeding the current value in μm.
As used herein, the term "specific surface area (BET)" means that a unit mass of material has a total surface area in m 2 /g。
As used herein, the term "gram capacity" means the amount of electricity that can be released per gram of positive electrode active material in milliamp hours per gram (mAh/g). In the present application, the gram volume value can be used as a reference index for measuring the energy density.
In some embodiments, the a material is selected from at least one of the following:
lithium iron manganese phosphate or lithium iron phosphate, the chemical formula is LiMn d Fe 1-d PO 4 D is more than or equal to 0 and less than or equal to 0.9; and
lithium vanadium phosphate of the chemical formula Li 3 V 2 (PO 4 ) 3 。
By further selecting the above materials as the material a, the positive electrode active material of the present application can be made more cost-effective, longer in cycle life, and excellent in safety performance. In some embodiments, the selected chemical formula is LiMn d Fe 1-d PO 4 Wherein optionally 0.1.ltoreq.d.ltoreq.0.9, more optionally 0.1.ltoreq.d.ltoreq.0.8, can be more advantageous for improving cycle life and gram capacity simultaneously.
In some embodiments, the Dv99 of the A material is < 31 μm, alternatively Dv 99. Ltoreq.28 μm, and alternatively Dv99 > 4.2 μm; more optionally 10 μm.ltoreq.Dv99.ltoreq.28 μm. The Dv99 of the material A is controlled in the range, so that the processing performance of the slurry of the material can be ensured on the basis of improving the performance of the positive electrode active material, the coating interface of the slurry on a current collector is more uniform, and the positive electrode plate and the battery performance can be further improved.
In some embodiments, the BET of the A material is 8m 2 /g to 26m 2 /g, optionally 10m 2 /g to 24m 2 /g, more optionally 10m 2 /g to 23m 2 And/g. By controlling the BET of the material A within the above range, the electrochemical reaction area can be effectively limited, so that the interfacial side reaction in the cyclic process is reduced and inhibited, the cyclic decay rate is reduced, and the cyclic life is prolonged.
In some embodiments, the particle surface of the a material may also have 0.5-5 wt%, alternatively 1-2 wt% of a carbon coating, based on the total weight of the a material. Through the carbon coating, the materials A and B can be mixed more uniformly, and after the materials A and B are mixed, the material particle conductive network is optimized, so that the resistance of the pole piece is reduced, and the gram capacity is ensured to be normally exerted.
In some embodiments, in the positive electrode active material of the present application, the B material is present in a mixing ratio of 3 to 50 wt% based on the total weight of the positive electrode active material. Mixing the B material with the a material in such a mixing ratio can give a positive electrode active material having an improved gram capacity as compared to the a material alone without significantly losing the cycle life advantage of the a material.
In some embodiments, optionally, the B material is present in a mixing ratio of 5 wt% to 30 wt%, based on the total weight of the positive electrode active material. Further selection of the mixing ratio range of the B material can further improve the gram capacity and/or cycle life of the positive electrode active material.
In some embodiments, for a chemical formula (ii) LiNi a Co b E 1-a-b O 2 A is more than or equal to 0.5 and less than or equal to 0.98, alternatively, a is more than or equal to 0.50 and less than or equal to 0.90, still alternatively, a is more than or equal to 0.50 and less than or equal to 0.88, and still more alternatively, a is more than or equal to 0.55 and less than or equal to 0.88; and/or 0.005.ltoreq.b.ltoreq.0.30, optionally 0.05.ltoreq.b.ltoreq.0.30, more optionally 0.05.ltoreq.b.ltoreq.0.20. By controlling a and B in the general formula of the material B within the above-described range, further improvement in the gram capacity and cycle life of the positive electrode active material obtained after mixing the material a with the material B is facilitated.
In some embodiments, for the above formula (ii) LiNi a Co b E 1-a-b O 2 Wherein a and B have the following relationship: k= (a+b)/(1-a-b), and 1.5.ltoreq.k.ltoreq.99, alternatively 1.5.ltoreq.k.ltoreq.19. By limiting the coefficient k to the above range, the gram capacity and/or cycle life can be further improved.
In some embodiments, the mixing ratio m of k to a material (based on the total weight of the positive electrode active material) has the following relationship: k.m.gtoreq.1, alternatively k.m.gtoreq.1.1, more alternatively k.m.gtoreq.1.6. When k×m is within the above range, the positive electrode active material has more beneficial gram capacity and cycle life.
Controlling a, B and k in the chemical formula of the material B within the above-described ranges can significantly improve the gram capacity and/or electron conductivity and ion conductivity of the positive electrode active material of the present application and/or kinetics of the material, without significantly losing the cycle life advantages of the material.
In some embodiments, the B material is LiNi a Co b Mn 1-a-b O 2 、LiNi a Co b Al 1-a-b O 2 、LiNi a Co b Mn c Al 1-a-b-c O 2 Or a combination thereof, a, b are as defined above, 0.01.ltoreq.c.ltoreq.0.34. By selecting the above-described B material, the gram capacity and/or cycle life of the positive electrode active material can be further improved.
In various embodiments of the application, the B material may be a monocrystalline or monocrystalline-like material, or may be a secondary particulate (or polycrystalline material).
In some embodiments, the B material is a single crystal or monocrystalline-like material, the particles of which have a Dv50 of 2 μm to 4.5 μm, alternatively 2.1 μm to 4.4 μm, more alternatively 3.5 μm to 4.4 μm.
In the case of single crystal or single-like materials, in some embodiments, the BET of the B material is 0.40m 2 /g to 1.20m 2 /g, optionally 0.55m 2 /g to 0.95m 2 /g, more optionally 0.55m 2 /g to 0.89m 2 /g。
In the case of a single crystal or a single-crystal-like material, the particle size and specific surface area of the material B are controlled within the above ranges, and the gram capacity of the positive electrode active material obtained after mixing can be improved. Specifically, the control of the B material within such a particle size range contributes to shortening the diffusion path and bulk diffusion resistance of lithium ions, reducing polarization of the material, and improving capacity exertion of the positive electrode active material of the present application.
In the case of single crystal or single-like materials, in some embodiments, dv99.ltoreq.18 μm for the B material, alternatively Dv99.ltoreq.16 μm, alternatively Dv99 > 4.4 μm, more alternatively 10.5 μm.ltoreq.Dv99.ltoreq.15 μm. By controlling Dv99 within the above range, the slurry processability of the positive electrode active material of the present application can be improved, and the positive electrode sheet and battery performance can be further improved.
Alternatively, in some embodiments, the B material is a secondary particle (or polycrystalline material) having a Dv50 of 3.5 μm to 13 μm, alternatively 3.5 μm to 12 μm.
In the case of secondary particles, in some embodiments, the BET of the B material is 0.31m 2 /g to 1.51m 2 /g, optionally 0.54m 2 /g to 1.51m 2 /g。
Typically, the primary particles that form the secondary particles by agglomeration have a primary particle average particle size range that is conventional in the art for such materials, e.g., 50-800nm.
In the case of secondary particles, by limiting the particle size of the B material to the above-described range, the diffusion path and bulk diffusion resistance of lithium ions can be shortened, polarization of the material can be reduced, and capacity exertion of the positive electrode active material of the present application can be improved. Further, by controlling the specific surface area, the interfacial side reaction can be reduced, and deterioration of the battery life due to consumption of active lithium can be reduced.
In the case of secondary particles, in some embodiments, the Dv99 of the B material is 10 μm to 25 μm. The control of the specific surface area can ensure that the secondary particles of the material B have good compactness, and avoid the deterioration of energy density caused by low overall compaction of the mixed system due to partial core-shell structure, poor compaction of the hollow material and the like.
As described above, by further selecting the material B and related parameters, the performance of the positive electrode active material of the present application can be further improved, for example, the gram capacity can be improved and the cycle life can be improved.
In some embodiments, the positive electrode active material of the present application is composed of one or more a materials and one or more B materials.
In some embodiments, the a material and the B material are mixed (e.g., stirred and mixed using a stirred tank) by a conventional physical mixing manner to obtain the positive electrode active material of the present application.
Positive electrode plate
In one embodiment of the present application, the present application provides a positive electrode sheet comprising a current collector and a sheet material layer disposed on at least one surface of the current collector, the sheet material layer comprising the positive electrode active material of the present application. The positive electrode plate provided by the application has the advantages of improved gram capacity, good cycle life and smaller resistance.
As an example, the positive electrode current collector has two surfaces opposing in its own thickness direction, and the positive electrode material layer is provided on either one or both of the two surfaces opposing the positive electrode current collector.
In some embodiments, the positive current collector may employ a metal foil or a composite current collector. For example, as the metal foil, aluminum foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base layer. The composite current collector may be formed by forming a metal material (aluminum, aluminum alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the positive electrode material layer may further optionally include a binder. As an example, the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), a vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a fluoroacrylate resin.
In some embodiments, the positive electrode material layer may further optionally include a conductive agent. As an example, the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, the positive electrode sheet may be prepared by: dispersing the above components for preparing the positive electrode sheet, such as the positive electrode active material, the conductive agent, the binder and any other components, in a solvent (such as N-methylpyrrolidone) to form a positive electrode slurry; and (3) coating the positive electrode slurry on a positive electrode current collector, and obtaining a positive electrode plate after the procedures of drying, cold pressing and the like.
Secondary battery, battery module, battery pack, and power consumption device
The secondary battery, the battery module, the battery pack, and the electric device of the present application are described below with appropriate reference to the accompanying drawings.
In one embodiment of the present application, there is provided a secondary battery including the positive electrode active material of the present application or the positive electrode tab of the present application.
In some embodiments, the secondary battery is a lithium ion secondary battery.
In general, a secondary battery includes a positive electrode tab, a negative electrode tab, an electrolyte, and a separator. During the charge and discharge of the battery, active ions are inserted and extracted back and forth between the positive electrode plate and the negative electrode plate. The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The isolating film is arranged between the positive pole piece and the negative pole piece, and mainly plays a role in preventing the positive pole piece and the negative pole piece from being short-circuited, and meanwhile ions can pass through the isolating film.
[ negative electrode sheet ]
The negative electrode tab includes a negative electrode current collector and a negative electrode material layer disposed on at least one surface of the negative electrode current collector, the negative electrode material layer including a negative electrode active material.
As an example, the anode current collector has two surfaces opposing in its own thickness direction, and the anode material layer is provided on either one or both of the two surfaces opposing the anode current collector.
In some embodiments, the negative electrode current collector may employ a metal foil or a composite current collector. For example, as the metal foil, copper foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base material. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the anode active material may employ an anode active material for a battery, which is well known in the art. As an example, the anode active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, and the like. The silicon-based material may be at least one selected from elemental silicon, silicon oxygen compounds, silicon carbon composites, silicon nitrogen composites, and silicon alloys. The tin-based material may be at least one selected from elemental tin, tin oxide, and tin alloys. However, the present application is not limited to these materials, and other conventional materials that can be used as a battery anode active material may be used. These negative electrode active materials may be used alone or in combination of two or more.
In some embodiments, the negative electrode material layer further optionally includes a binder. The binder may be at least one selected from Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), sodium Polyacrylate (PAAs), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium Alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS).
In some embodiments, the negative electrode material layer further optionally includes a conductive agent. The conductive agent is at least one selected from superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
In some embodiments, the negative electrode material layer may also optionally include other adjuvants, such as thickening agents (e.g., sodium carboxymethyl cellulose (CMC-Na)), and the like.
In some embodiments, the negative electrode sheet may be prepared by: dispersing the above components for preparing the negative electrode sheet, such as a negative electrode active material, a conductive agent, a binder and any other components, in a solvent (e.g., deionized water) to form a negative electrode slurry; and coating the negative electrode slurry on a negative electrode current collector, and obtaining a negative electrode plate after the procedures of drying, cold pressing and the like.
[ electrolyte ]
The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The application is not particularly limited in the kind of electrolyte, and may be selected according to the need. For example, the electrolyte may be liquid, gel, or all solid.
In some embodiments, the electrolyte is an electrolyte. The electrolyte includes an electrolyte salt and a solvent.
In some embodiments, the electrolyte salt may be selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bis-fluorosulfonyl imide, lithium bis-trifluoromethanesulfonyl imide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalato borate, lithium difluorodioxaato phosphate, and lithium tetrafluorooxalato phosphate.
In some embodiments, the solvent may be selected from at least one of ethylene carbonate, propylene carbonate, methylethyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, 1, 4-butyrolactone, sulfolane, dimethyl sulfone, methyl sulfone, and diethyl sulfone.
In some embodiments, the electrolyte further optionally includes an additive. For example, the additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives capable of improving certain properties of the battery, such as additives that improve the overcharge performance of the battery, additives that improve the high or low temperature performance of the battery, and the like.
[ isolation Membrane ]
In some embodiments, a separator is further included in the secondary battery. The type of the separator is not particularly limited, and any known porous separator having good chemical stability and mechanical stability can be used.
In some embodiments, the material of the isolating film may be at least one selected from glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride. The separator may be a single-layer film or a multilayer composite film, and is not particularly limited. When the separator is a multilayer composite film, the materials of the respective layers may be the same or different, and are not particularly limited.
In some embodiments, the positive electrode tab, the negative electrode tab, and the separator may be manufactured into an electrode assembly through a winding process or a lamination process.
In some embodiments, the secondary battery may include an outer package. The outer package may be used to encapsulate the electrode assembly and electrolyte described above.
In some embodiments, the outer package of the secondary battery may be a hard case, such as a hard plastic case, an aluminum case, a steel case, or the like. The exterior package of the secondary battery may also be a pouch type pouch, for example. The material of the flexible bag may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, and polybutylene succinate.
The shape of the secondary battery is not particularly limited in the present application, and may be cylindrical, square, or any other shape. For example, fig. 1 is a secondary battery 5 of a square structure as one example.
In some embodiments, referring to fig. 2, the outer package may include a housing 51 and a cover 53. The housing 51 may include a bottom plate and a side plate connected to the bottom plate, where the bottom plate and the side plate enclose a receiving chamber. The housing 51 has an opening communicating with the accommodation chamber, and the cover plate 53 can be provided to cover the opening to close the accommodation chamber. The positive electrode tab, the negative electrode tab, and the separator may be formed into the electrode assembly 52 through a winding process or a lamination process. The electrode assembly 52 is enclosed in the accommodating chamber. The electrolyte is impregnated in the electrode assembly 52. The number of electrode assemblies 52 included in the secondary battery 5 may be one or more, and those skilled in the art may select according to specific practical requirements.
In one embodiment of the present application, there is provided a battery module including the secondary battery of the present application.
In some embodiments, the secondary batteries may be assembled into a battery module, and the number of secondary batteries included in the battery module may be one or more, and the specific number may be selected by one skilled in the art according to the application and capacity of the battery module.
Fig. 3 is a battery module 4 as an example. Referring to fig. 3, in the battery module 4, a plurality of secondary batteries 5 may be sequentially arranged in the longitudinal direction of the battery module 4. Of course, the arrangement may be performed in any other way. The plurality of secondary batteries 5 may be further fixed by fasteners.
Alternatively, the battery module 4 may further include a case having an accommodating space in which the plurality of secondary batteries 5 are accommodated.
In one embodiment of the present application, a battery pack is provided that includes the battery module of the present application.
In some embodiments, the above battery modules may be further assembled into a battery pack, and the number of battery modules included in the battery pack may be one or more, and a specific number may be selected by those skilled in the art according to the application and capacity of the battery pack.
Fig. 4 and 5 are battery packs 1 as an example. Referring to fig. 4 and 5, a battery case and a plurality of battery modules 4 disposed in the battery case may be included in the battery pack 1. The battery box includes an upper box body 2 and a lower box body 3, and the upper box body 2 can be covered on the lower box body 3 and forms a closed space for accommodating the battery module 4. The plurality of battery modules 4 may be arranged in the battery box in any manner.
In addition, the application also provides an electric device which comprises at least one of the secondary battery, the battery module or the battery pack. The secondary battery, the battery module, or the battery pack may be used as a power source of the power consumption device, and may also be used as an energy storage unit of the power consumption device. The power utilization device may include mobile devices (e.g., cell phones, notebook computers, etc.), electric vehicles (e.g., electric-only vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but is not limited thereto.
As the electricity consumption device, a secondary battery, a battery module, or a battery pack may be selected according to the use requirements thereof.
Fig. 6 is an electrical device as an example. The electric device is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle or the like. In order to meet the high power and high energy density requirements of the secondary battery by the power consumption device, a battery pack or a battery module may be employed.
As another example, the device may be a cell phone, tablet computer, notebook computer, or the like. The device is generally required to be light and thin, and a secondary battery can be used as a power source.
Examples
Hereinafter, embodiments of the present application are described. The following examples are illustrative only and are not to be construed as limiting the application. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The method comprises the following steps:
1. method for manufacturing secondary battery
(1) Preparing a positive electrode plate:
the materials a and B in the following examples (the numbers are indicated by numerals, for example, example 1) and comparative examples (the numbers are indicated by "C + numerals", for example, comparative example C1) were stirred and mixed in a stirring apparatus (such as a stirring tank), and the resultant mixture was used as the positive electrode active material of the present application. The mixing proportion M of the a material is a weight percentage based on the total weight of the positive electrode active material, m=m A /(M A +M B +mc … …) 100%, where M A 、M B The respective components of Mc and Mc are the masses of a material a, B, C (if any), and the like, which are used for mixing to obtain a positive electrode active material.
Adding positive electrode active material, binder polyvinylidene fluoride (PVDF) and conductive carbon Super-P into solvent N-methyl pyrrolidone (NMP) to make the mass ratio of positive electrode active material, PVDF and conductive carbon be 90:5:5, stirring them in drying room to obtain uniform slurry with viscosity of 3000-10000 mPa.S, then placing it on aluminium foil at 20mg/cm 2 The slurry is coated on the load capacity of the anode plate, and the anode plate is manufactured through drying and cold pressing.
(2) Preparing a negative electrode plate:
artificial graphite is used as a cathode active material, and is added into deionized water together with sodium carboxymethylcellulose (CMC), conductive carbon Super-P and Styrene Butadiene Rubber (SBR) according to the mass ratio of 94:1.5:2:2.5, and the mixture is stirred in a drying room to prepare uniform slurry with the viscosity of 2000-12000 mPa.S. The slurry is then coated onto a current collector copper foil with a coating quality to form a coated pole piece. The coated pole piece is dried and cold-pressed to prepare the negative pole piece.
The coating quality is calculated by the following relation:
94% of coating mass of negative electrode graphite gram capacity=1.15×90% of coating mass of positive electrode [ (x1×w1+x2×w2)/(w1+w2) ];
wherein,
the gram capacity of graphite is 350mAh/g,
x1 and x2 are the gram capacities of materials a and B respectively as measured by the following "electrical testing of lithium half cell powder button",
w1 and w2 are the blending ratios of the a material and the B material, respectively (weight percentages based on the total weight of the positive electrode active material obtained by blending).
(3) Electrolyte solution:
LiPF6 was added to a mixture of Ethylene Carbonate (EC), diethyl carbonate (DEC) and dimethyl carbonate (DMC) in a volume ratio of 1:1:1 to prepare a 1mol/L solution, and 5wt.% fluoroethylene carbonate (FEC) was added to obtain an electrolyte. Here, the FEC was added in a weight percentage based on the total weight of the electrolyte.
(4) Isolation film:
a porous film made of Polyethylene (PE) was used as a separator.
(5) Preparation of secondary battery:
the secondary battery is assembled for testing through processes of pole piece punching, pole lug cleaning, lamination, welding, top sealing, liquid injection, preforming, air extraction, forming and the like in a drying room.
2. Powder buckling test method for lithium half battery
The material to be tested (for example, A material or B material) (in powder form), the binder polyvinylidene fluoride (PVDF) and conductive carbon Super-P are added into solvent N-methyl pyrrolidone (NMP) so that the mass ratio among the material to be tested, PVDF and conductive carbon is 90:5:5. Stirring in a drying room with a refiner (Froude, germany, R30A) to obtain a uniform slurry with a viscosity of 3000 to 10000 mPa.S, and then applying 20mg/cm on aluminum foil 2 The slurry is coated on the load capacity of the anode plate, and the anode plate is manufactured through drying and cold pressing.
Positive electrode sheet and PP separator (Celgard, 2400), metallic lithium sheet (Tianjin lithium energy, diameter 15.6mm, thickness 450 μm, purity > 99.9%) and 100 μl electrolyte (electrolyte is prepared by adding LiPF6 to a mixture of Ethylene Carbonate (EC), diethyl carbonate (DEC) and dimethyl carbonate (DMC) in volume ratio of 1:1:1 to prepare a 1mol/L solution, adding 5wt.% fluoroethylene carbonate (FEC) thereto), assembling a button-to-lithium half cell with CR 2032 button cell assembly (available from the family of the general road, 304 stainless steel) in a glove box (braun, ar atmosphere), taking the half cell out of the glove box, standing for 12h at ambient temperature, and then performing capacity test as follows:
The test instrument adopts CT2001A blue electricity (blue electric blue river), the prepared lithium half battery is stood for 5min under the constant temperature environment of 25 ℃, then the lithium half battery is discharged to 2.5V according to 1/3C (C represents the charge-discharge capacity multiplying power, 1C represents the current intensity of complete discharge after 1 hour, the charge-discharge multiplying power of the battery=charge-discharge current/rated capacity; C can be directly understood as nominal capacity herein), and then the lithium half battery is charged to 4.35V or 4.3V according to the constant current and constant voltage of 1/3C after being stood for 5min (wherein, when the material B is LiNi in chemical formula a Co b E 1-a-b O 2 When a is less than or equal to 0.7, the upper limit voltage of charge is 4.35V; and when the B material is LiNi a Co b E 1-a-b O 2 When a is more than 0.7 or is a secondary particle (polycrystalline material), the upper limit voltage of charge is 4.30V), then constant voltage charge is carried out at 4.35V or 4.3V until the current is less than or equal to 0.05mA, and the charge capacity is recorded as C0 when the charge is left for 5 min; then, the discharge capacity was set to 2.5V at 1/3C0, and the initial discharge capacity was designated as D0.
The initial gram capacity of the measured material sample was calculated for each material sample separately according to the following formula:
initial gram capacity=d0 of the measured material/mass of the measured cell corresponds to the mass of the positive electrode active material.
And testing and calculating initial gram capacity of 5 parallel samples, removing the highest and lowest values from the initial gram capacity, and taking an average value of the rest 3 data to obtain the initial gram capacity of the material to be tested.
In the above formula, "the mass of the battery cell to be measured corresponding to the positive electrode active material" is determined according to the "positive electrode sheet active material mass test" hereinafter.
3. Method for testing quality of active substance of positive pole piece
The positive electrode piece to be measured is punched into a circular sheet with the diameter of 14mm to be used as a sample to be measured (calculated to be 154mm in approximate area 2 ) And simultaneously, punching a wafer with the diameter of 14mm serving as a blank sample by using the current collector for preparing the pole piece to be tested.
The total weight of the 20 blank samples is obtained by weighing, and the average mass m of the blank samples (namely the current collector of the pole piece) is obtained by dividing the total mass by the corresponding number 0 The unit is gram (g). Respectively weighing 20 samples to be measured, and sequentially marking as m 1 、m 2 、m 3 ……m 20 The unit is g.
The length of the positive pole piece of the laminated battery core prepared by the pole piece is a, the width is b, and the unit is mm; the mass of the active material of the positive electrode plate of the laminated battery cell is calculated as follows:
active mass=90% { [ (m) 1 +m 2 +m 3 ……+m 20 )/20]-m 0 }*(a*b)/154。
4. Initial gram capacity test method for positive electrode active material in secondary battery
The test instrument used a CT 4000-5V6A Xinwei machine (Xinweil electronics Co., ltd.). The secondary battery prepared as described above was left standing for 5min at a constant temperature of 25 ℃ respectively, then discharged to 2.5V according to 1/3C (C represents charge-discharge capacity ratio, 1C represents current intensity after complete discharge for 1 hour, charge-discharge ratio=charge-discharge current/rated capacity; herein, C may also be directly understood as nominal capacity), and then charged to 4.3V or 4.25V according to a constant current and constant voltage of 1/3C after standing for 5min (wherein, when the B material is of the formula LiNi) a Co b E 1-a-b O 2 When a is less than or equal to 0.7, the upper limit voltage of charge is4.3V; and when the B material is LiNi a Co b E 1-a-b O 2 When a is more than 0.7 or is a secondary particle (polycrystalline material), the upper limit voltage of charge is 4.25V), then the single crystal or the material similar to single crystal is charged to current which is less than or equal to 0.05mA under the constant voltage of 4.3V or 4.25V respectively, and the material is kept stand for 5min, and the charge capacity at the moment is marked as C0'; then, the discharge capacity was set to 2.5V at 1/3C0', and the initial discharge capacity was designated as D0'.
The initial gram capacity of the positive electrode active material was calculated for each secondary battery sample according to the following formula:
initial gram capacity of positive electrode active material = D0'/mass of positive electrode active material;
wherein "mass of positive electrode active material" is determined according to method 3 above.
And testing and calculating initial gram capacity of 5 parallel samples, removing the highest value and the lowest value from the initial gram capacity, and taking an average value from the rest 3 data to obtain the initial gram capacity of the secondary battery to be tested.
5. Method for testing cycle performance of secondary battery at 25 DEG C
The test instrument used a CT 4000-5V6A Xinwei machine (Xinweil electronics Co., ltd.). Each secondary battery prepared as described above was subjected to a test voltage of 2.5 to 4.3V or 2.5 to 4.25V in a constant temperature environment at 25 ℃ (wherein, in the material B LiNi a Co b E 1-a-b O 2 In the case where a > 0.7 or the material is a secondary particle (polycrystal), the test voltage is 2.5 to 4.25V; and when a is less than or equal to 0.7 and the material is single crystal or quasi-single crystal, the test voltage is 2.5 to 4.3V), the battery is charged to 4.3V or 4.25V according to 0.5C0' (C0 ' is measured in the initial gram capacity test method of secondary battery), then the battery is charged to current less than or equal to 0.05mA under constant voltage of 4.3V or 4.25V, and the battery is left stand for 5min, and then discharged to 2.5V according to 0.5C0', which is one cycle, and the discharge capacity is recorded as D1; the above operation was repeated, and the discharge capacity for n cycles was recorded as D n (n=1, 2, 3.). Calculate the degree of cell attenuation (State of health, SOH) =d n /D 3 *100%. Recording cell capacity fadeThe number of cycles of the secondary battery to be tested up to 70% SOH was used as an index for examining the cycle ability.
And (5) testing the parallel samples, removing the highest value and the lowest value of the cycle number, and taking the average value of the rest 3 samples to obtain the cycle number of the secondary battery to be tested when the final battery capacity is attenuated to 70% SOH.
In the present application, the measured cycle number is processed in whole 5 to whole 10 based on the test accuracy + -5. Specifically, the data processing method is as follows: the actual number of cycles measured is divided by 5 to obtain the quotient and (if any) the remainder. When the remainder is more than or equal to 3, the recorded circle number is (quotient 5+5); when the remainder is < 3, the number of recorded cycles is (quotient 5) cycles.
6. Pole piece resistance testing method
The testing instrument is a GDW3-KDY-2 two-probe diaphragm resistance tester (Huitian Chengzheng technology in Beijing). Taking the positive electrode piece prepared in the method 1 (1), and preparing a sample of 4cm x 25 cm. The sample should have good appearance (i.e., the interface of the pole piece sample is uniform, and there are no obvious phenomena of color difference, metal leakage, decarburization, powder falling, scratch, etc.). The sample was vacuum dried at 85 ℃ for more than 4 hours and tested using the resistance tester described above. The test pressure was 0.2-0.4MPa, 20 parallel samples were tested, sample data acquisition time t=15 s (since the resistance meter data showed about 15s for stability). And (5) taking all the measured resistance data as a box diagram, and taking the median of the box diagram to obtain the pole piece resistance.
7. Powder laser granularity testing method
Referring to national standard GB/T19077-2016, a Mastersizer 3000 laser diffraction particle size analyzer (Mark Paraco) was used, in which deionized water was used as the solvent, and the positive electrode active material to be tested was sonicated for 5min before testing.
By this test, the particle size distribution of the material, typically Dv10, dv50, dv90, dv99 and their distribution curves, can be obtained. In the application, the method is mainly used for measuring the particle size distribution of monocrystalline or monocrystalline-like particles and secondary particles.
8. Specific surface area (BET) test method
With reference to GB/T19587-2004, specific surface area tests were carried out on various powdered materials involved in the present application with a specific surface area porosity analyzer TRISTAR II 3020 (American microphone instruments Co.). Before testing, the powder is dried in a vacuum oven at 200 ℃ for more than or equal to 2 hours, and the required powder amount is more than 20g.
9. Primary particle size testing method
The various powdery materials related to the application are tested by a sigma 300 scanning electron microscope (zeiss company), the test sample and the magnification are adjusted to enable the field of view to have more than 100 primary particles, the size of the particles in the length direction is measured by a scale, 100-200 primary particles are measured in total, then 1/10 of particles with the maximum particle size and 1/10 of particles with the minimum particle size are removed from the particles, and the average particle size is obtained by averaging the particle size data of the remaining 8/10 of particles. The particle size range of the primary particles constituting the secondary particles was confirmed in this way.
10. Powder compaction density testing method
Referring to GB/T24533-2009 test, a powder compaction density tester (model: YT-101F) was used, the powder sample amount was 1.0g, and the parallel samples were tested 3-5 times.
The calculation formula of the compaction density is as follows:
pC＝m/V＝m/(S*H)
Wherein:
pC- -the compacted density of the powder in g/cm;
m-sample mass in g;
s- -die bottom area, in this context, the test die was set to a value of 1.327cm depending on the equipment used 2 ；
H- -compacted thickness in cm.
Examples 1 to 7 and comparative examples C1 to 3
In examples 1-7 and comparative examples C1-3, the A material was LiMn 0.6 Fe 0.4 PO 4 (LMFP material), single crystal material, dv50 of 1.1 μm, dv99 of 25 μm, BET of 21m 2 G, g capacity is 140mAh/g; the materials B are LiNi 0.55 Co 0.12 Mn 0.33 O 2 (NCM material), a monocrystalline (or quasi-monocrystalline) material, a Dv50 of 4.2 μm, a Dv99 of 10.5 μm, and a BET of 0.55m 2 G, g capacity is 170mAh/g.
Table 1 below shows the gram capacity and cycle life (25 ℃) of the positive electrode active material obtained by mixing the a and B materials in different mixing ratios. The respective mixing ratios in the following table 1 are weight percentages based on the total weight of the a material and the B material.
TABLE 1
As can be seen from table 1, the positive electrode active materials of examples 1 to 7, which were obtained by mixing not less than 50 wt%, particularly 50 wt% to 97 wt%, of the a material with the B material, have improved gram capacity and/or cycle performance, compared to the use of the a material alone (comparative example C1). In particular, the positive electrode active material obtained by mixing the a material with the B material at a mixing ratio m of, optionally, 65 to 97% by weight, more optionally, 70 to 97% by weight, still more optionally, 80 to 97% by weight has an improved gram capacity and/or higher cycle performance than the case of using the a material alone.
Examples 8 to 16
In the following, table 2 shows lithium iron phosphate or a different lithium iron manganese phosphate material (of the general chemical formula LiMn d Fe 1-d PO 4 ) Performance data of the positive electrode active material prepared by mixing with NCM as the B material. Wherein, in the following respective examples, the B material (chemical formula is LiNi 0.55 Co 0.12 Mn 0.33 O 2 ) All have the following parameters: the gram capacity was 170mAh/g, the Dv50 was 4.2. Mu.m, the Dv99 was 10.5. Mu.m, and the BET was 0.55m 2 And/g. Wherein, in the following respective examples, the mixing ratio m of the A materials was 80% by weight and the mixing ratio of the B materials was 20% by weight, based on the total weight of the positive electrode active material。
TABLE 2
As can be seen from Table 2, when the formula LiMn of the A material is d Fe 1-d PO 4 In the above, d has a value in the range of 0 to 0.9, and the positive electrode active material obtained after mixing with the B material has an improved gram capacity and a good cycle life. When the material a is a lithium iron manganese phosphate material, the positive electrode active material of the present application has both improved gram capacity and cycle life and has both higher gram capacity and cycle life values when d has a value of 0.1 to 0.9, optionally in the range of 0.1 to 0.8 in the above chemical formula.
Examples 17 to 31 and comparative examples C5 to C6
The material A is selected from the following materials or a mixture thereof: liMn 0.6 Fe 0.4 PO 4 (denoted by LMFP in Table 3), liFePO 4 (shown as LFP in Table 3) and Li 3 V 2 (PO 4 ) 3 (indicated as LVP in table 3); and, in the following table 3, when the a material is a mixture of the above materials, it is expressed as, for example, lfp+lmfp (i.e., liMn 0.6 Fe 0.4 PO 4 With LiFePO 4 Is a mixture of (a) and (b).
In example 24, the A material was an LFP material (gram capacity 145mAh/g, dv50 1 μm, dv99 10 μm, and BET 23 m) 2 Per g) and LMFP materials (g capacity 140mAh/g, dv50 of 1.1 μm, dv99 of 25 μm, and BET of 21 m) 2 And/g) the mixture obtained is mixed in a weight ratio of 1:1.
In example 25, the A material was an LFP material (gram capacity 145mAh/g, dv50 1 μm, dv99 10 μm, and BET 23 m) 2 Per g) and LMFP materials (g capacity 140mAh/g, dv50 of 1.1 μm, dv99 of 25 μm, and BET of 21 m) 2 /g) are mixed in a weight ratio of 2:8 to giveIs a mixture of (a) and (b).
The material B is selected from the following monocrystalline or monocrystalline-like materials or mixtures thereof: liNi 0.55 Co 0.12 Mn 0.33 O 2 (represented by NCM in Table 3), liNi 0.55 Co 0.12 Mn 0.18 Al 0.15 O 2 (represented by NCMA-1 in Table 3), liNi 0.55 Co 0.12 Mn 0.31 Al 0.02 O 2 (represented by NCMA-2 in Table 3), liNi 0.55 Co 0.12 Mn 0.03 Al 0.3 O 2 (represented by NCMA-3 in Table 3), liNi 0.55 Co 0.15 Mn 0.15 Al 0.15 O 2 (indicated as NCMA-4 in Table 3). In each of the following examples, the a material was blended with the B material in a blending ratio m of 80 wt%, based on the total weight of the positive electrode active material.
In example 26, the B material was an NCM material (170 mAh/g in gram capacity, 4.2 μm in Dv50, 10.5 μm in Dv99, and 0.55m in BET) expressed as above 2 Per g) and NCMA-4 material (g capacity 172mAh/g, dv50 3.9 μm, dv99 11.0 μm, and BET 0.65 m) 2 And/g) the mixture obtained is mixed in a weight ratio of 1:1.
Table 3 below shows the gram capacity and cycle life (25 ℃) of the positive electrode material obtained by mixing a and B materials having different Dv50 and/or Dv99 and/or BET. Each mixing ratio is a weight percentage based on the total weight of the positive electrode active material.
As can be seen from table 2, when Dv50 of the a material is in the range of 0.8 μm to 4.2 μm, the positive electrode active material of the present application can have both good gram capacity and cycle life, i.e., the cycle life is not significantly lost while the gram capacity is increased, compared to the use of the a material alone. However, when the amount is outside this range, the resultant positive electrode active material has poor overall properties (i.e., uneven properties) (for example, when the Dv50 is 0.7 μm, the gram capacity is improved but the cycle life is greatly reduced to an unacceptable level) and such a material is not practically useful. In particular, the positive electrode active material of the present application has improved gram capacity and longer cycle life when Dv50 of the a material is in the range of 0.9 μm to 2.3 μm, optionally 1 μm to 1.5 μm.
Examples 32 to 54 and comparative examples C7 to C11
In the following examples 32 to 54 and comparative examples C7 to C11, the A material was LiMn 0.6 Fe 0.4 PO 4 (LMFP in Table 4), single crystal material, dv50 of 1.1 μm, dv99 of 25 μm, BET of 21m 2 Per g, g capacity 140mAh/g, cycle life 3570 cycles. In each of the examples and comparative examples of table 4, the mixing proportion m of the a material was 80 wt% based on the total weight of the positive electrode active material.
The material B is LiNi a Co b Mn 1-a-b O 2 Wherein the particles of monocrystalline material have a Dv50 of 2.7-5.6 μm, a Dv99 of 5.4-34.5 μm and a BET of 0.45-1.05m 2 /g; the particles (i.e., secondary particles) of the polycrystalline material have a Dv50 of 9.2 to 12.5 μm, a Dv99 of 20 to 30.5 μm, and a BET of 0.32 to 0.54m 2 And/g. The primary particle size of the secondary particles formed by agglomeration is 50-800nm. The mixing proportion of the B material was 20% by weight based on the total weight of the positive electrode active material.
Table 4 below shows the gram capacity and cycle life (25 ℃) of the resulting positive electrode material, mixed with a material a and B having different values of a and B, and different values of k x m.
As can be seen from Table 6 above, when the B material is a single crystal material, the crystal particles thereof have a Dv50 of 2 to 4.5. Mu.m, alternatively 2.1 to 4.5. Mu.m, and/or a Dv99 of 10.5 to 21. Mu.m, and/or a BET of 0.40 to 1.20m 2 /g, optionally 0.41-1.19m 2 The positive electrode active material of the present application has improved gram capacity and good cycle life (i.e., no significant loss of cycle life advantage of the a material) when compared to the a material alone at/g. Optionally, the Dv50 is 2.1-4.4 μm and/or the BET is 0.55-0.95m 2 The positive electrode active material of the present application has an improved gram capacity and a higher cycle life than the a material alone at/g. More optionally, the Dv50 is 3.5-4.4 μm and/or the BET is 0.55-0.89m 2 The positive electrode active material of the present application has a simultaneously improved gram capacity and cycle life when compared to the use of the a material alone.
When the B material is a polycrystalline material (i.e., secondary particles each having an average particle diameter of primary particles constituting the secondary particles in the range of 50 to 800nm as determined by scanning electron microscopy), when Dv50 is 3.5 to 13 μm, and/or Dv99 is 10 to 25 μm, and/or BET is 0.31 to 1.51m 2 The positive electrode active material of the present application has an improved gram capacity and longer cycle life than the a material alone at/g. Alternatively, when the Dv50 is 3.5-12 μm and/or the BET is 0.54-1.51m 2 At/g, the cathode active material of the present application has improved gram capacity and cycle life compared to the a material alone.
The present application is not limited to the above embodiment. The above embodiments are merely examples, and embodiments having substantially the same configuration and the same effects as those of the technical idea within the scope of the present application are included in the technical scope of the present application. Further, various modifications that can be made to the embodiments and other modes of combining some of the constituent elements in the embodiments, which are conceivable to those skilled in the art, are also included in the scope of the present application within the scope not departing from the gist of the present application.
Claims (15)
- A positive electrode active material comprising an a material as described below and a B material as described below, whereinThe material A is at least one selected from the following materials:Li x M y (PO 4 ) zwherein M is selected from one or more of Ni, co, mn, fe, mg, al, V, zn, zr, F, x is not less than 1 and not more than 3, z is not less than 1 and not more than 3, v is the valence of M, and x+vy-3 z=0;the material A is monocrystalline material or monocrystalline-like material;the Dv50 of the a material is 0.8 μm to 4.2 μm, alternatively 0.8 μm to 3.2 μm, more alternatively 0.9 μm to 2.3 μm, still more alternatively 1 μm to 1.5 μm;the material B is at least one of the following materials:(i)LiAO 2 A is Ni, co or Mn; and(ii)LiNi a Co b E 1-a-b O 2 e is selected from at least one of Mn and Al, a is more than or equal to 0.50 and less than or equal to 0.98,0.001, b is more than or equal to 0.3;the a material is present in a mixing proportion m of 50 to 97 wt%, alternatively 65 to 97 wt%, more alternatively 70 to 95 wt%, and still more alternatively 80 to 95 wt%, based on the total weight of the positive electrode active material.
- The positive electrode active material according to claim 1, wherein the B material is present in a mixing proportion of 3 to 50 wt%, optionally 5 to 30 wt%, based on the total weight of the positive electrode active material.
- The positive electrode active material according to claim 1 or 2, wherein the a material is selected from at least one of:lithium iron manganese phosphate or lithium iron phosphate, the chemical formula is LiMn d Fe 1-d PO 4 D is more than or equal to 0 and less than or equal to 0.9, alternatively, d is more than or equal to 0.1 and less than or equal to 0.9, and still more alternatively, d is more than or equal to 0.1 and less than or equal to 0.8; andlithium vanadium phosphate of the chemical formula Li 3 V 2 (PO 4 ) 3 。
- The positive electrode active material according to any one of claims 1 to 3, wherein the specific surface area of the a material is 8m 2 /g to 26m 2 /g, optionally 10m 2 /g to 24m 2 /g, more optionally 10m 2 /g to 23m 2 /g。
- The positive electrode active material according to any one of claims 1 to 4, wherein (ii) LiNi of the B material a Co b E 1-a-b O 2 Wherein a is more than or equal to 0.5 and less than or equal to 0.98, alternatively, a is more than or equal to 0.50 and less than or equal to 0.90, more alternatively, a is more than or equal to 0.50 and less than or equal to 0.88, and still more alternatively, a is more than or equal to 0.55 and less than or equal to 0.88; and/or 0.005.ltoreq.b.ltoreq.0.30, optionally 0.05.ltoreq.b.ltoreq.0.30, more optionally 0.05.ltoreq.b.ltoreq.0.20.
- The positive electrode active material according to any one of claims 1 to 5, wherein (ii) LiNi of the B material a Co b E 1-a-b O 2 Wherein a and b have the following relationship:k= (a+b)/(1-a-b), and 1.5.ltoreq.k.ltoreq.99, alternatively 1.5.ltoreq.k.ltoreq.19.
- The positive electrode active material according to claim 6, wherein the k and m have the following relationship: k.m.gtoreq.1, alternatively k.m.gtoreq.1.1, more alternatively k.m.gtoreq.1.6.
- The positive electrode active material according to any one of claims 1 to 7, wherein (ii) LiNi of the B material a Co b E 1-a-b O 2 Is LiNi a Co b Mn 1-a-b O 2 、LiNi a Co b Al 1-a-b O 2 、LiNi a Co b Mn c Al 1-a-b-c O 2 Or a combination thereof, a and b are as defined in claim 1, and 0.01.ltoreq.c.ltoreq.0.34.
- The positive electrode active material according to any one of claims 1 to 8, wherein the B material is a single crystal or a single-crystal-like material, the particles of which have a Dv50 of 2 μm to 4.5 μm, optionally 2.1 μm to 4.4 μm, more optionally 3.5 μm to 4.4 μm; and/or a specific surface area of 0.40m 2 /g to 1.20m 2 /g, optionally 0.55m 2 /g to 0.95m 2 /g, more optionally 0.55m 2 /g to 0.89m 2 /g。
- The positive electrode active material according to any one of claims 1 to 8, wherein the B material is a secondary particle having a Dv50 of 3.5 to 13 μιη, optionally 3.5 to 12 μιη; and/or a specific surface area of 0.31m 2 /g to 1.51m 2 /g, optionally 0.54m 2 /g to 1.51m 2 /g。
- A positive electrode sheet comprising a current collector and a layer of a sheet material disposed on at least one surface of the current collector, the layer of material sheet comprising the positive electrode active material of any one of claims 1 to 10.
- A secondary battery comprising the positive electrode active material according to any one of claims 1 to 10 or the positive electrode tab according to claim 11.
- A battery module comprising the secondary battery according to claim 12.
- A battery pack comprising the battery module of claim 13.
- An electric device comprising at least one selected from the secondary battery of claim 12, the battery module of claim 13, or the battery pack of claim 14.
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| JP2007317534A (en) * | 2006-05-26 | 2007-12-06 | Sony Corp | Non-aqueous electrolyte secondary battery |
| JP5381024B2 (en) * | 2008-11-06 | 2014-01-08 | 株式会社Ｇｓユアサ | Positive electrode for lithium secondary battery and lithium secondary battery |
| US20120231341A1 (en) * | 2011-03-09 | 2012-09-13 | Jun-Sik Kim | Positive active material, and electrode and lithium battery containing the positive active material |
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